New dyestuff of the thioindigo series



Patented Sept. 20, 1932 UNITED STATES TION OF DELAWARE PATENT OFFICEERWIN HOFFAIANID HANS HEYNA, or FRANxroR'r-oN-T E-MAI -HocHsT,GERMANY,

ASSIGNORS TO GENERAL ANILINE worms, INC., on NEW YORK, N. Y., A CORPORA-N EW DYE ST'UFF OF THE THIOINIDIGO SERIES Ho Drawing. Application filedMay 5, 1930, Serial No. 450,054, and in Germany May 18, 1929.

' Thepresent invention relates to new dye- .stufis' of thethioindigo'series. 1

V More particularly our invention is concerned with the dyestuffs of thefollowing general formula:

wherein Hlg stands for halogen,

Z and Z are different 'substituents and Z may stand for halogen, methylor hydrogen and Z for halogen or hydrogen. Processes of preparing ournew compounds are obvious from their chemical structure.

A preferred method comprises coupling such particularly valuable for useas printing colors. I 1 Among the above defined class of new dye stuffsthe compounds of the following general formula are of particularinterest:

wherein Z; and Z are different substituents and Z may stand forchlorine, methyl or hydrogen and Z for chlorine or hydrogen.

The fastness to light of these dyestuffs is remarkable.

The starting materials are obtainable by I converting such3-halogenphenyl-1-thioglycolic acids as are substituted in the2-position by a carboxylic acid group, a cyano group or a carboxy-amidegroup according to one of the known methods into the correspondinghydroxythionaphthene compounds.

The following examples are intended to illustrate our invention withoutlimiting it, all parts being by weight: v

(1) 10 parts of 3-chlorophenyl-1-thioglycol-2-carboxylic acid are heatedfor about 1 hour under reflux with 50 parts-0f acetic acid I anhydridein the presence of 2 parts of anhydrous sodium acetate. From thereaction mass the acetic acid anhydride and acetic acidare distilledoff, whereafter the 4-chloro- 3-acetyloxythionaphthene is saponified andthe hydroxythionaphthene is then isolated as usual. It has the meltingpoint of about 119 C.120 C. It is oxydized according to known methodswhereby the dyestuff of the following. probable formula:

1 I oo oo is obtained. It'forms a red-violet powder and yield on cottonred tints of excellent f-astness to light. V V3-chlorophenyl-1-thioglycol -=2 carboxylic acid to be used according tothese examples as starting material can be prepared by diazotizing6-chloro-2-amino-l-benzoic acid, converting the diazo compound thusobtained into the xanthogenate ester, sapomfylng 111 an alkalinemediumand condensing the mer-' captane thus obtained withchloro-ac-etic acid.(2) 32 parts of 4-methyl-6-chloro-2.3

diketo dihyrdothionaphthenequinone -2 (pdimethylamine)-anile are heatedto'boiling with 18.5 parts of. 1'-chloro-3-hydroxythionaphthene in 600parts of aceticacidl The dyestuff thus obtained corresponds with thefollowing probable formula:

. 01.. g V I,

00 CO D It is isolated by filtering the reaction mass and washing toneutral reaction. It dyes cotton parts by weight of 4e-chloro-3- thefollowing p on I and dyes cotton red tints o'l excellent fa. to light.

(4) 28.5 parts of el-methyl-QB-diketo-dihydrothionaphthene quinone 2(p-dimethylamine -anile e. heated to boi n w h 18.0

naphthene in abOutGOO parts of tCQLl untl the formation of the s i finThe react' .11 mass after h. n filtered oil a .d washed to no Thedycstuff thus obtained cor i robable formula o l o o o o It yields oncotton red tints or e1 ness to light.

e claimt: 1. As new products, the compounds of the followin g probableformula:

Hlg 0 o Z1,

wherein Hlg stands for halogen,

Z and Z are dillerent substituents and Z may stand for halogen, methylor hydrogen and V Z for halogen or hydrogen, being dyestuffs possessinggood fmtness properties especiallyto light and yielding on cotton cleartints.

2. As new products, the compounds of the following probable formula:

Cl 0 O 1,

wherein Z and Z are different substituents and Z may stand for chlorine,methyl or hy drogen and fetal-e5. and it corresponds Z for chlorine orhydrogen, being dyestuffs possessing good fastness properties especiallyto light and yielding on cotton clear tints.

3. As new products'the compounds of the following probable formulayestuffs possessing good fastness propo washing and Very good l astnessto light and yielding on cotton clear red tints. As a new product, thecompound of the A following probable formula:

Cl 0 H g dyestull' possessing excellent fastness light and yielding oncotton new product the compound of the probable formula ng in the drystate a. red-yiolet'powder' red tints of excellent fastness to .dlLMlIS.

tures. I ERVVIN HOFFA. HANS HEYNA;

lloj

In testimony whereof, we our signa-

